Tuning h‐bond capability of hydroxylated‐poly(2,3,4,5,6‐pentafluorostyrene) grafted copolymers prepared by chemoselective and versatile thiol‐para‐fluoro “click‐type” coupling with mercaptoalcohols

Abstract

Novel H‐bond donor copolymers were designed by a versatile “click type” grafting reaction of unprotected mercaptoalcohols onto poly(2,3,4,5,6‐pentafluorostyrene) (PPFS). As demonstrated by 19F NMR and Fourier transform infrared spectroscopy (FTIR) analyses, the reaction appears to be chemoselective as the SH groups solely react onto the para‐fluoro position of the PFS units. The nucleophilic substitution was successfully performed with two mercaptoalcohols bearing either one or two hydroxyl groups. By carefully selecting the experimental conditions, a library of copolymers with various degree of substitution up to 95% was obtained in a reasonable timescale through kinetic control. By turbidity analysis, the ability of these functional polymers to form in solution interpolymer complexes with poly(4‐vinyl pyridine) was shown to be tunable by adjusting the molecular characteristics. FTIR, X‐ray photoelectron spectroscopy, and Differential scanning calorimetry evidence that different types of blends (immiscible, partially or totally miscible, and complex) can be achieved, and that the driving force of the interaction originates from H‐bond. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012

Enhancement of Localized Surface Plasmon Resonance polymer based biosensor chips using well-defined glycopolymers for lectin detection

“…Unfortunately, it was discovered that the substitution efficiency dropped significantly for longer PPFS chains and a large excess (>2 eqv) of thioglucose was required to achieve a sufficiently satisfactory substitution percentage for this study. A reasonable explanation was given by Chen et al who pointed out that the strong hydrogen-bonding between free and substituted thioglucose molecules reduces the nucleophilicity of free thioglucose and resulted in a retardation effect for the substitution reaction [33]. In order to achieve higher substitution efficiencies, glycosylation of the P2, P3 and P4 samples were carried out using acetylated thioglucose (P2-GluAc, P3-GluAc, P4-GluAc respectively) followed by deprotection of the acetyl groups to afford the desired glycopolymers (P2-GluOH, P3-GluOH, P4-GluOH respectively) [16].…”

Self‐Propagated para‐Fluoro‐Thiol Reaction

“…Furthermore, as nucleophilic substitution reactions are enhanced in more polar solvents, the influence of the solvent on PFTR was investigated for each thiol. Specifically, polar protic solvents were excluded as the solvent would most likely form hydrogen bonds with the nucleophilic thiol, and thus retard the PFTR.…”

An emerging post‐polymerization modification technique: The promise of thiol‐para‐fluoro click reaction

“…It is also emphasized that degree of substitution strongly depends on the polarity of the solvent. Low substitution degree was found when a less polar solvent such as ethyl acetate was used whereas a high substitution degree was found when a more polar solvent such as methyl ethyl ketone was used …”